CN117488377B - Preparation method and application of leveling agent for electroplating - Google Patents
Preparation method and application of leveling agent for electroplating Download PDFInfo
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- CN117488377B CN117488377B CN202311847834.1A CN202311847834A CN117488377B CN 117488377 B CN117488377 B CN 117488377B CN 202311847834 A CN202311847834 A CN 202311847834A CN 117488377 B CN117488377 B CN 117488377B
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- electroplating
- leveling agent
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- diglycidyl ether
- heterocyclic compound
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- 238000009713 electroplating Methods 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 20
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005956 quaternization reaction Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 238000011049 filling Methods 0.000 claims description 24
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 17
- -1 1, 2-dimethyl imidazole cation Chemical group 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000002608 ionic liquid Substances 0.000 claims description 11
- 230000005855 radiation Effects 0.000 claims description 8
- WAXJKRAXMPVMEA-UHFFFAOYSA-N 1-butyl-2,3-dimethyl-1,2-dihydroimidazol-1-ium;dihydrogen phosphate Chemical compound OP(O)([O-])=O.CCCC[NH+]1C=CN(C)C1C WAXJKRAXMPVMEA-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 3
- NOYXQFBTCCSKQG-UHFFFAOYSA-N 2-[[2-(oxiran-2-ylmethoxy)cyclohexyl]oxymethyl]oxirane Chemical compound C1OC1COC1CCCCC1OCC1CO1 NOYXQFBTCCSKQG-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 150000001350 alkyl halides Chemical class 0.000 claims description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 2
- 229940073608 benzyl chloride Drugs 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 150000008050 dialkyl sulfates Chemical class 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 16
- 239000007795 chemical reaction product Substances 0.000 abstract description 8
- 238000005429 filling process Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 238000007747 plating Methods 0.000 description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 18
- 229910052802 copper Inorganic materials 0.000 description 18
- 239000010949 copper Substances 0.000 description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 9
- 239000000080 wetting agent Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- BFFQFGGITJXTFP-UHFFFAOYSA-N 3-methyldioxetane Chemical compound CC1COO1 BFFQFGGITJXTFP-UHFFFAOYSA-N 0.000 description 5
- BVTJGGGYKAMDBN-UHFFFAOYSA-N Dioxetane Chemical compound C1COO1 BVTJGGGYKAMDBN-UHFFFAOYSA-N 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- 238000005282 brightening Methods 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- KHAZIIVSIJPRGF-UHFFFAOYSA-N [Na].CCCS Chemical compound [Na].CCCS KHAZIIVSIJPRGF-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- MLMGJTAJUDSUKA-UHFFFAOYSA-N 2-ethenyl-1h-imidazole Chemical compound C=CC1=NC=CN1 MLMGJTAJUDSUKA-UHFFFAOYSA-N 0.000 description 2
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001768 cations Chemical group 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000003541 multi-stage reaction Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 description 2
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical compound [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229940108925 copper gluconate Drugs 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
Abstract
The invention relates to a preparation method and application of a leveling agent for electroplating, and belongs to the technical field of electroplated metal. The global PCB industry production value is rapidly increased in proportion to the total production value of the electronic component industry, is the industry with the largest proportion in the electronic component subdivision industry, and has unique position. The volume of the electronic product is gradually reduced, and the direct overlapping of the through blind holes is a design method for obtaining high-density interconnection. To make the stacked holes, the flatness of the bottom of the holes should be made first. There are several typical methods for fabricating flat hole surfaces, and the electroplating hole filling process is a representative one. The invention uses two or more heterocyclic compounds and diglycidyl ether to react step by step, and the product obtained by the reaction is subjected to quaternization, so that the reaction product can be directly used for electroplating without separate purification.
Description
Technical Field
The invention belongs to the technical field of electroplated metal, and relates to a preparation method and application of a leveling agent for electroplating.
Background
The global PCB industry production value is rapidly increased in proportion to the total production value of the electronic component industry, is the industry with the largest proportion in the electronic component subdivision industry, and has unique position. The volume of the electronic product is gradually reduced, and the direct overlapping of the through blind holes is a design method for obtaining high-density interconnection. To make the stacked holes, the flatness of the bottom of the holes should be made first. There are several typical methods for fabricating flat hole surfaces, and the electroplating hole filling process is a representative one.
Besides reducing the necessity of additional process development, the electroplating hole filling process is compatible with the existing process equipment, and is beneficial to obtaining good reliability. The electroplating solution comprises an electroplating composition comprising copper ions, an acid, an aldehyde, a halogen, a brightening agent, a leveling agent, and a wetting agent.
Leveling agents are typically nitrogen-containing organic substances that have the primary function of adsorbing at the high current density areas (raised areas or corners) and slowing the plating rate at that point without affecting the plating at the low current density areas (recessed areas), thereby leveling the surface, which is an essential additive in plating. Generally, the plating hole filling adopts a high-copper low-acid system to roughen the plating layer, and researches show that the problem of poor plating layer can be effectively solved by adding the leveling agent.
As circuit board lines become finer, hole filling performance requirements become more difficult. Heretofore, it has been known that the synthesis of a leveling agent comprising a reaction condensate of an amine with a glycidyl ether or a quaternary ammonium derivative of the condensate, a reactant of a compound such as imidazole with a polyepoxide compound having an ether bond, a reaction product of an amine with epichlorohydrin or epibromohydrin, or the like, can fill blind holes having a pore diameter of 75/90/100/115 μm and a pore depth of 75 μm, and can achieve a pore-filling depression value of less than 5 μm under low-temperature low-current density conditions. On the one hand, in the case of the through holes with relatively large thickness diameters in recent years, the blind holes with the hole depth of more than 100 μm and the blind holes with the hole diameter of more than 125 μm are difficult to be filled well in the prior art. On the other hand, the reaction process in the prior art is complex, and the process flow is complex. The prior art either needs to strictly control the temperature to be 0 ℃ or needs to be 80 ℃ or even 90 ℃, so that the actual operation difficulty is high and the control is difficult. The product needs to be purified in a complex way, has low yield and is not beneficial to industrial production. Overall, the prior art has the following drawbacks:
1. the reaction temperature in the synthesis process is too low or too high to control, resulting in uneven molecular weight distribution of the product.
2. The leveling agent synthesized in the prior art needs complex purification, has low yield and is not beneficial to industrial production.
3. The leveling agent is synthesized by reacting a nitrogen-containing compound with a glycidyl ether, and the reaction product is single.
4. The yield of tertiary amine compounds generated by the ring-opening reaction of more than three glycidyl ethers is low, the subsequent quaternization is affected, and the industrialization is not facilitated.
5. Aiming at the plates with the aperture larger than 125 mu m, the hole filling effect is poor, the hole filling concave value is larger than 10 mu m, the hole filling rate is lower than 80%, and the manufacture of the large-aperture plates is limited.
6. The electroplating difference with the through holes of the plate during hole filling electroplating can not meet the requirement.
7. The through hole plate with a larger thickness-diameter ratio has poor deep plating capability.
8. The plating surface has high copper thickness and high cost, and is unfavorable for the production operation after copper plating.
Disclosure of Invention
The invention aims to provide a preparation method and application of a leveling agent for electroplating.
The aim of the invention can be achieved by the following technical scheme:
a preparation method of a leveling agent for electroplating comprises the following preparation processes: two or more heterocyclic compounds and diglycidyl ether are used for stepwise reaction, the product obtained by the reaction is subjected to quaternization, the reaction product is not required to be purified independently, can be directly used for electroplating,
the stepwise reaction flow is as follows:
s1: adding a first heterocyclic compound into diglycidyl ether, adding 1-1.2 wt% of catalyst (calculated by mass of the whole system), heating and reacting by taking deionized water as a solvent, wherein the reaction temperature is 25-80 ℃ and the reaction time is 2-3 hours, the diglycidyl ether is one or more selected from 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether and 1, 2-cyclohexanediol diglycidyl ether, and the first heterocyclic compound is one or more selected from imidazole, 1-methylimidazole and benzimidazole;
the preparation flow of the catalyst is as follows,
introducing butyl at the 2-position of 1, 2-dimethyl imidazole cation to obtain a modified intermediate bromo-1-butyl-2, 3-dimethyl imidazole, and mixing with KPF 6 Synthesizing 1-butyl-2, 3-dimethyl imidazole phosphate ionic liquid under the assistance of microwave radiation, and washing the obtained product with distilled water to remove impurities;
s2: adding a second heterocyclic compound, wherein the second heterocyclic compound and the first heterocyclic compound are two different heterocyclic rings, more than two compounds can be prepared in the reaction process, the reaction temperature is 25-80 ℃, the reaction time is 4-5 hours, and the second heterocyclic compound is one or more selected from pyridine, 1,2, 4-triazole, piperidine and 2-vinylimidazole;
wherein, the mol ratio of the two heterocyclic compounds to the diglycidyl ether is (2-2.5): 1, the molar ratio of the first heterocyclic compound to the second heterocyclic compound is (1-1.5): 1.
the mixed nitrogen-containing compound is used for reacting with the diglycidyl ether in the invention, and the reaction of the single-component nitrogen-containing compound and the diglycidyl ether in the prior art can be replaced. Two nitrogen-containing compounds can respectively carry out ring-opening reaction with two epoxy groups of diglycidyl ether, at least one more reaction product can exist, which plays an important role in copper ion accumulation during electroplating, so that the plating layer is smoother and more compact, and the potential difference between the inside of the regulating hole and the copper surface is positively improved, thereby promoting the hole filling effect and the electroplating effect in the through hole.
Further, the product produced in S2 is subjected to a quaternization reaction by reacting the product produced in S2 with a quaternizing agent selected from one or more of methyl iodide, benzyl chloride, dialkyl sulfate in water.
Further, the quaternization reaction steps are as follows: dissolving the product obtained by the step reaction in water, stirring and dissolving at 25 ℃, adding methyl iodide, heating to 40-90 ℃, reacting for 12-36 hours, naturally cooling to room temperature, continuously aging for 1-6 hours, and carrying out suction filtration to obtain the quaternary ammonium salt product.
Further, the quaternization reaction is in a weak alkaline environment, and the weak alkalinity of the solution is maintained in the aging process.
Further, the microwave radiation auxiliary parameters in the preparation of the catalyst are as follows: the radiation power is 300W, the haloalkane content is 2 wt percent, and the radiation time is 3 min.
The ionic liquid catalyst has wide operating temperature range, the using temperature range is-40-300 ℃, and the ionic liquid catalyst has good thermal stability and chemical stability, is easy to separate from other substances and can be recycled. The ionic liquid catalyst is used in the invention, so that the reaction rate can be improved, the structural formulas of reaction products are more various, and products with different configurations are ensured to be generated.
The hydrogen at the 2-position of the imidazole cation has activity,can be combined with OH in alkaline environment - The reaction produces carbenes, so that the activity of the hydrogen in the 2-position of the cation is firstly eliminated by modification. The modification method is to introduce an alkyl group at the No. 2 position, and as the structure of cations influences the property of the ionic liquid, longer butane is introduced to increase the Van der Waals force between ions, so that the ionic liquid is more stable.
Further, the molecular weight of the diglycidyl ether is selected from 200-240.
The leveling agent for electroplating is applied to electroplating liquid, and can be used for filling blind holes with the size of 125 mu m, 150 mu m or 165 mu m in large holes.
Two or more nitrogen-containing compounds and diglycidyl ether react step by step with water as solvent at 25-80 ℃ for 4-8h, and the reaction products can be directly used for electroplating without separate purification. Compared with the prior art, the method has the advantages that the nitrogen-containing compound reacts with triglycidyl ether at the temperature of 0 ℃, the condition is mild and easy to control, the obtained product has good copper plating flatness, good copper plating effect in holes, the surface copper is lower than 15 mu m, the aperture filling rate of 70/80/90/100 mu m is more than 95%, and the aperture filling rate of 110/120/130/140/150 mu m is more than 90%.
The quaternization product has the advantages, and the quaternization process is simple and easy to operate. The prior art has the disadvantages that the nitrogen-containing compound and more than three glycidyl ethers need to react below 0 ℃, the operation condition is high, the synthesis is difficult, and the method is not suitable for industrial production. Compared with the prior art, the reaction in the invention can be completed at 50 ℃, and then the quaternization is carried out, the quaternization temperature is 50 ℃, the synthesis is easy, and the operation is more convenient.
Drawings
The present invention is further described below with reference to the accompanying drawings for the convenience of understanding by those skilled in the art.
FIG. 1 is a cross-sectional view of a 150 μm/75 μm pore-filling in example 1;
FIG. 2 is a cross-sectional view of a 100 μm/75 μm pore-filling in comparative example 1;
FIG. 3 is a cross-sectional view of a 125 μm/75 μm pore-filling in comparative example 1;
FIG. 4 is a cross-sectional view of a 0.2cm/1.2cm through hole in comparative example 1;
FIG. 5 is a cross-sectional view of 0.2cm/1.6cm through-hole plating in comparative example 2;
FIG. 6 is a cross-sectional view of a 150 μm/75 μm pore-filling in comparative example 3;
FIG. 7 is a cross-sectional view of a 125 μm/70 μm fill hole in comparative example 4.
Detailed Description
In order to further describe the technical means and effects adopted by the invention for achieving the preset aim, the following detailed description is given below of the specific implementation, structure, characteristics and effects according to the invention with reference to the attached drawings and the preferred embodiment.
The electroplating solution is prepared by the following steps:
copper ion, acid, aldehyde, halogen, brightening agent, leveling agent and wetting agent.
Copper ions: copper sulfate, copper chloride, copper acetate, copper nitrate, copper alkyl sulfonate, copper gluconate, and the like, with copper sulfate being preferred. 50-300g/L, preferably 70-250g/L.
Acid: sulfuric acid, acetic acid, methanesulfonic acid, fluoroboric acid, tartaric acid, formic acid, and the like, with sulfuric acid being preferred. 50-300g/L, preferably 70-250g/L.
Halogen: chloride, iodide, bromide, etc., preferably chloride. 10 to 100ppm, preferably 30 to 80ppm.
And (3) brightening agent: sodium polydithio-propane sulfonate, sodium phenyl-disulfide-propane sulfonate, sodium alkoxide-sulfur propane sulfonate, sodium polydimethyl amide sulfonate, 3-mercapto-2-propane acid, etc., preferably sodium polydithio-propane sulfonate. 0.1 to 100ppm, preferably 1 to 50ppm
Leveling agent: the compositions according to the invention are in the range from 10 to 1000ppm, preferably from 100 to 500ppm.
Wetting agent: polyethylene glycol, sodium lauryl sulfate, polyethers, copolymers of ethylene oxide and propylene oxide, polyethylenimine, quaternary ammonium salts thereof, polyethylenimine alkyl salts, and the like, with polyethylene glycol being preferred. 10-1000ppm, preferably 100-600ppm.
Electroplating experiment:
electroplating solution: 230g/L copper sulfate, 40g/L sulfuric acid, 45ppm chloride ion, 1ppm brightening agent, 100ppm leveling agent and 500ppm wetting agent. 100/125/150 mu m/75 mu m blind hole plate material, current density of 1 asd-2.5 asd and plating copper of 10-20 mu m.
230g/L sulfuric acid, 80g/L copper sulfate, 45ppm chloride ion, 1ppm brightener, 100ppm leveler and 500ppm wetting agent. A through hole plate with a pore diameter of 200 mu m/250 mu m/300 mu m/350 mu m and a pore depth of 1500 mu m has a current density of 1.5 asd-2.5 asd and a plating surface copper of 15-25 mu m.
Example 1:
synthesis of leveler 1: 70mmol of imidazole, 90mmol of 1, 4-butanediol diglycidyl ether are dissolved in 120ml of deionized water, 10mmol of 1-butyl-2, 3-dimethyl imidazole phosphate ionic liquid serving as a catalyst is added, 30mmol of pyridine is added after the reaction is carried out for 2 hours at 50 ℃, the reaction is continued for 6 hours at 50 ℃, and the reaction product in the step is obtained after suction filtration and washing. 20g of the synthesized product of the step is weighed and dissolved in 80ml of water, 11g of methyl iodide is added and reacted for 24 hours at 50 ℃. Filtering, washing to obtain leveling agent 1, and verifying by infrared spectrum FTIR to obtain Ji Anfeng 1680cm product -1 。
Electroplating hole filling experiment: the electroplating solution comprises the following components: 230g/L of copper sulfate pentahydrate, 40g/L of sulfuric acid, 45ppm of chloride ions, 1ppm of 3-mercaptopropane sodium sulfonate, 300ppm of EO/PO block polyether (oxyethylene ether and oxypropylene ether) as wetting agents, and the molecular weight is less than 8000. 50ppm leveler 1. Blind hole plates with a diameter of 75/100/125/150/165 μm and a depth of 75 μm were electroplated in a halin bath, with through holes simultaneously present in the blind hole plates. The electroplating conditions are as follows: the current density is 2asd, the electroplating time is 50min, and the electroplating temperature is 25 ℃. The copper plated sections were observed by a metallographic microscope. FIG. 1 is a sectional view of a plated hole of 150 μm/75 μm with a dishing value of 3 μm and a porosity of 96%.
Comparative example 1:
synthesis of leveler 2: 60mmol of 1-methylimidazole, 100mmol of 1, 6-hexanediol diglycidyl ether (epoxy value 0.65-0.7) are dissolved in 120ml of deionized water, then 10mmol of 1-butyl-2, 3-dimethylimidazole phosphate ionic liquid as a catalyst is added, 60mmol of 1,2, 4-triazole is added after reaction for 2 hours at 50 ℃, reaction is continued for 6 hours at 50 ℃, suction filtration and washing are carried out, quaternization reaction is not carried out in the embodiment, a leveling agent 2 is obtained, and characteristic peaks (2.54, 2.71 and 3.08 ppm) of epoxide and infrared spectrum FTIR epoxy groups are confirmed by nuclear magnetic resonance NMRGroup characteristic peak 912-916cm -1 Disappearance was used to verify the completion of the reaction. All reactants were quantified to 1000ml in a volumetric flask.
Electroplating hole filling experiment: the electroplating solution comprises the following components: 230g/L of copper sulfate pentahydrate, 40g/L of sulfuric acid, 45ppm of chloride ions, 1ppm of 3-mercaptopropane sodium sulfonate, 300ppm of EO/PO block polyether (oxyethylene ether and oxypropylene ether) as wetting agents, and the molecular weight is less than 8000. 100ppm leveler 2. Blind hole plates with a diameter of 75/100/125/150/165 μm and a depth of 75 μm were electroplated in a halin bath, with through holes simultaneously present in the blind hole plates. The electroplating conditions are as follows: the current density is 2asd, the electroplating time is 50min, and the electroplating temperature is 25 ℃. The copper plated sections were observed by a metallographic microscope. FIG. 2 is a cross-sectional view of a 100 μm/75 μm electroplated hole filling with a dishing value of 2 μm and a uniform and knotless hole filling copper plating. FIG. 3 is a sectional view of a plated hole of 125 μm/75 μm with a dent value of 4 μm and a porosity of 94%. FIG. 4 is a view of an electroplated section of a via hole under a fill condition, with a depth capability TP of 75%.
Comparative example 2:
through hole electroplating experiments: the electroplating solution comprises the following components: 75g/L copper sulfate pentahydrate, 230g/L sulfuric acid, 45ppm chloride ion, 1ppm sodium 3-mercaptopropane sulfonate, 300ppm EO/PO block polyether (oxyethylene ether and oxypropylene ether), and molecular weight less than 8000. 100ppm leveler 2. The diameter of the hole is 0.2mm, and the through hole plate with the thickness of the base material plate being 1.6cm is electroplated in the Halin groove. The electroplating conditions are as follows: the current density is 2asd, and the electroplating time is 50min. The copper plated sections were observed by a metallographic microscope. FIG. 5 is a cross-sectional view after plating, with surface copper of about 20 μm, hole copper of about 18 μm, thickness to diameter ratio of 8 to 1, and deep plating capability TP of 87%.
Comparative example 3:
synthesis of leveler 3: 60mmol of imidazole, 100mmol of 1, 6-hexanediol diglycidyl ether (epoxy value 0.65-0.7) is dissolved in 120ml of deionized water, then 10mmol of 1-butyl-2, 3-dimethyl imidazole phosphate ionic liquid serving as a catalyst is added, 60mmol of piperidine is added after the mixture is reacted for 2 hours at 50 ℃, the reaction is continued for 6 hours at 50 ℃, the mixture is filtered and washed by suction, the quaternization reaction is not carried out in the embodiment, the leveling agent 3 is obtained, and all reactants are quantified to 1000ml by a volumetric flask.
Electroplating hole filling experiment: the electroplating solution comprises the following components: 230g/L of copper sulfate pentahydrate, 40g/L of sulfuric acid, 45ppm of chloride ions, 1ppm of 3-mercaptopropane sodium sulfonate, 300ppm of EO/PO block polyether (oxyethylene ether and oxypropylene ether) as wetting agents, molecular weight of less than 8000, 30 ppm of leveling agent 1 and 70ppm of leveling agent 3 were added. Blind hole plates with a diameter of 75/100/125/150/165 μm and a depth of 75 μm were electroplated in a halin bath, with through holes simultaneously present in the blind hole plates. The electroplating conditions are as follows: the current density is 2asd, the electroplating time is 50min, and the electroplating temperature is 25 ℃. The copper plated sections were observed by a metallographic microscope. FIG. 6 is a cross-sectional view of a 125 μm/75 μm electroplated hole filling with a dishing value of less than 5 μm and a hole filling rate of greater than 95%.
Comparative example 4:
synthesis of leveler 4: 100mmol of benzimidazole, 200mmol of 1, 2-cyclohexanediol diglycidyl ether (epoxy value 0.59-0.64) are dissolved in 120ml of deionized water, catalyst 1-butyl-2, 3-dimethylimidazole phosphate ionic liquid 15mmol is added, 85mmol of 2-vinylimidazole is added after reaction for 3 hours at 50 ℃, reaction is continued for 5 hours at 60 ℃, suction filtration and washing are carried out, quaternization reaction is not carried out in the embodiment, leveling agent 4 is obtained, and all reactants are quantified to 1000ml by a volumetric flask.
Electroplating hole filling experiment: the electroplating solution comprises the following components: 220g/L copper sulfate pentahydrate, 45g/L sulfuric acid, 50ppm chloride ions, 3ppm sodium 3-mercaptopropane sulfonate, 600ppm EO/PO block polyether (oxyethylene ether and oxypropylene ether) as wetting agent, and molecular weight less than 8000. 300ppm leveler 4. Blind well plates having a diameter of 100/115/125/140/150 μm and a depth of 70 μm were plated in a halin tank. The electroplating conditions are as follows: the current density is 2asd, the electroplating time is 50min, the electroplating temperature is 25 ℃, and the copper plating section is observed by a metallographic microscope. FIG. 7 is a sectional view of a plated hole of 125 μm/70 μm with a dishing value of 3 μm and a porosity of 95% or more.
The invention is used when in use:
the present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (6)
1. The preparation method of the leveling agent for electroplating is characterized in that the preparation process of the leveling agent comprises the following steps of:
s1: adding a first heterocyclic compound into diglycidyl ether, adding 1-1.2 wt% of catalyst, and heating to react by taking deionized water as a solvent, wherein the reaction temperature is 25-80 ℃ and the reaction time is 2-3 hours, the diglycidyl ether is one or more selected from 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether and 1, 2-cyclohexanediol diglycidyl ether, and the first heterocyclic compound is one or more selected from imidazole, 1-methylimidazole and benzimidazole;
the preparation flow of the catalyst is as follows,
introducing butyl at the 2-position of 1, 2-dimethyl imidazole cation to obtain a modified intermediate bromo-1-butyl-2, 3-dimethyl imidazole, and mixing with KPF 6 Synthesizing 1-butyl-2, 3-dimethyl imidazole phosphate ionic liquid under the assistance of microwave radiation, and washing the obtained product with distilled water to remove impurities;
s2: adding a second heterocyclic compound, wherein the second heterocyclic compound and the first heterocyclic compound are two different heterocyclic rings, more than two compounds can be prepared in the reaction process, the reaction temperature is 25-80 ℃, the reaction time is 4-5 h, and the second heterocyclic compound is selected from pyridine;
wherein, the mol ratio of the two heterocyclic compounds to the diglycidyl ether is (2-2.5): 1, the molar ratio of the first heterocyclic compound to the second heterocyclic compound is (1-1.5): 1.
2. the method for producing a leveling agent for electroplating according to claim 1, wherein the product produced in S2 is subjected to a quaternization reaction by reacting the product produced in S2 with a quaternizing agent selected from one or more of methyl iodide, benzyl chloride, dialkyl sulfate in water.
3. The method for preparing a leveling agent for electroplating according to claim 2, wherein the quaternization reaction step is as follows: dissolving the product obtained by the step reaction in water, stirring and dissolving at 25 ℃, adding methyl iodide, heating to 40-90 ℃, reacting for 12-36 hours, naturally cooling to room temperature, continuously aging for 1-6 hours, and carrying out suction filtration to obtain the quaternary ammonium salt product.
4. The method for preparing a leveling agent for electroplating according to claim 1, wherein the auxiliary parameters of microwave radiation in the preparation of the catalyst are as follows: the radiation power is 300W, the haloalkane content is 2 wt percent, and the radiation time is 3 min.
5. The method for preparing a leveling agent for electroplating according to claim 1, wherein: the diglycidyl ether has a molecular weight of 200-240.
6. The use of a leveling agent for electroplating according to any one of claims 1-5, wherein the leveling agent for electroplating is used in electroplating solution for filling blind holes with a pore size of 125 μm, 150 μm or 165 μm.
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